CN109880654A - A method of utilizing volatile matter Fischer Tropsch waxes in low-order coal - Google Patents
A method of utilizing volatile matter Fischer Tropsch waxes in low-order coal Download PDFInfo
- Publication number
- CN109880654A CN109880654A CN201910105628.0A CN201910105628A CN109880654A CN 109880654 A CN109880654 A CN 109880654A CN 201910105628 A CN201910105628 A CN 201910105628A CN 109880654 A CN109880654 A CN 109880654A
- Authority
- CN
- China
- Prior art keywords
- gas
- low
- order coal
- reforming
- coal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 227
- 239000003245 coal Substances 0.000 title claims abstract description 140
- 239000001993 wax Substances 0.000 title claims abstract description 64
- 239000007789 gas Substances 0.000 claims abstract description 217
- 230000008569 process Effects 0.000 claims abstract description 144
- 238000002309 gasification Methods 0.000 claims abstract description 84
- 238000002407 reforming Methods 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 62
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 60
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 54
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 52
- 238000001035 drying Methods 0.000 claims abstract description 47
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 30
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 241000772415 Neovison vison Species 0.000 claims abstract description 19
- 238000005516 engineering process Methods 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 239000000428 dust Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- 230000000694 effects Effects 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000001833 catalytic reforming Methods 0.000 claims description 9
- 238000005262 decarbonization Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008246 gaseous mixture Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 238000012797 qualification Methods 0.000 claims description 4
- -1 hydrocarbon Hydrocarbon Chemical class 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 230000009467 reduction Effects 0.000 abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 27
- 239000003921 oil Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 235000019198 oils Nutrition 0.000 description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 239000011280 coal tar Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000003502 gasoline Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000004880 explosion Methods 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000010687 lubricating oil Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000011269 tar Substances 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229920000856 Amylose Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 235000019476 oil-water mixture Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OGGDTCDHYILUIN-UHFFFAOYSA-N C(O)CN.C(C)(=S)O Chemical compound C(O)CN.C(C)(=S)O OGGDTCDHYILUIN-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000000061 acid fraction Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides a kind of methods using volatile matter Fischer Tropsch waxes in low-order coal, low-order coal passes sequentially through drying, gasification reduction treatment obtains gas mixture, and gasification reducing process is the chemical reaction process heated under anaerobic or micro-oxygen conditions to the low-order coal after drying；Gas mixture is purified to obtain mixed gas；Mixed gas is obtained through the reforming process of some hydrocarbon comprising CO and H2Reforming gas, reforming qi exhaustion remove CO2Mend H again afterwards2Or CO obtains the synthesis gas that hydrogen-carbon ratio is 1.5-2.2；Synthesis gas carries out F- T synthesis under the action of catalyst and obtains hydrocarbon mixture and tail gas through Oil-gas Separation, and hydrocarbon mixture obtains wax, mink cell focus and naphtha through distillate stripping etc..Volatile matter in low-order coal is used to produce light oil, mink cell focus and wax, convenient transportation by present invention application F- T synthesis technology, to improve the utilization rate of resource；And raw material sources of the present invention are extensive, and process energy consumption is low, is conducive to save production cost.
Description
Technical field
The present invention relates to volatile matter Fischer-Tropsch in coal substance clean utilization technical field more particularly to a kind of utilization low-order coal to close
At the method for wax.
Background technique
China is the country of a rich coal, oil-poor, few gas, and consumption of coal accounts for 60% or more of non-renewable energy consumption figure,
Which dictates that the energy resource structure based on coal is difficult to change within the quite a long time.In terms of explored coal mine quality,
The middle low-order coal proportion in China is very big, thus low-order coal production high-quality chemical products are aobvious in rationally and efficiently utilizing
It obtains particularly important.
China at present to coal resources by the way of means it is relatively simple, only simple burning obtains burning therein
Chemical energy, this simple Land use systems are not only the huge waste to energy resources, and the various productions generated of burning
Object can also serious ground contamination environment.According to the national conditions and energy resource structure situation of China at this stage, the coal that China is rich in and natural
The problem of gas resource is converted into more convenient transport and more environmentally-friendly liquid fuel on the spot, not only can solve the wasting of resources, together
When can also contribute to the enhancement of environment in China.
Coal produces fuel oil through F- T synthesis and chemicals is one of the important content in clean coal technology field.F- T synthesis
It is the chemical process that coal gas is transformed into higher hydrocarbon, is non-petroleum carbon containing resource (coal, natural gas, residual oil and biology
Matter etc.) Efficient Conversion utilize most important approach.Coal gas generates a series of the advanced of different carbon numbers under the effect of the catalyst
Hydrocarbon, while obtaining some low-carbon alkenes and alcohols etc..Head product obtains the oil products such as gasoline, diesel oil and second after further treatment
The chemicals such as alkene, propylene, lubricating oil and paraffin.The product that the iron-based slurry bed system of Fischer-Tropsch comes out is based on gasoline, diesel oil.Gasoline is come
Say, the gasoline possible alternative in China very much (such as ethanol petrol, methanol gasoline, MTG thioacetic acid monoethanolamine, natural gas,
LPG liquefied petroleum gas).Especially country is formulating relevant criterion in the recent period, widelys popularize the application of replacing gasoline.Therefore, it adopts
Being synthetically produced gasoline with Fischer-Tropsch is not optimal path.It is high with the rapid development of the automotive industry with the enhancing of environmental protection consciousness
Shelves lubricating oil ratio shared in the market share is increasing, and high-quality feed of base oil is in long term structural shortage shape
State.The saturation degree of soft wax is high in F- T synthesis crude product, hardly sulfur-bearing, nitrogen, aromatic hydrocarbons, is to prepare top-grade lubricating oil base oil not
Quality raw materials that can be more, have considerable commercial interest.
Summary of the invention
In view of this, in view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of utilize in low-order coal to volatilize
The method for dividing Fischer Tropsch waxes, by the way that the volatile matter gasification reduction in low-order coal is obtained gas mixture, by gas mixture
Purified treatment is removed impurity and is obtained comprising H2, CO and hydro carbons mixed gas, using catalytic reforming by the hydro carbons in mixed gas
It is reforming to increase H in mixed gas2Volume basis with CO by synthesis gas using F- T synthesis technology always than being used to produce
Light oil, mink cell focus and wax etc., added value of product is high, is conducive to transport, to improve the utilization rate of resource；And the present invention is former
Expect from a wealth of sources, process energy consumption is low, is conducive to save production cost.
In order to solve the above technical problems, the present invention provides the following technical scheme that
A method of using volatile matter Fischer Tropsch waxes in low-order coal, low-order coal passes sequentially through stoving process and gasification also
Original process handle to obtain gas mixture, and the gasification reducing process is under anaerobic or micro-oxygen conditions to the low-order coal after drying
The chemical reaction process heated；
The purified technique of gas mixture is obtained comprising CO, H2With the mixed gas of hydro carbons；
The mixed gas is obtained through the reforming process of some hydrocarbon comprising CO and H2Reforming gas, it is described
Reforming gas handles to obtain synthesis gas by decarbonization process, by supplementing CO or H2The hydrogen-carbon ratio of the synthesis gas is adjusted to
1.5-2.2；
The synthesis gas carries out Fischer-Tropsch synthesis under fischer-tropsch synthetic catalyst effect and obtains through Oil-gas Separation technique
Thick mink cell focus, thick light oil, heavy wax and tail gas, the thick mink cell focus, thick light oil and heavy wax are through distillate stripping process
Mink cell focus, naphtha and lightweight wax are obtained, the lightweight wax handles to obtain product qualification wax through wax filtering technique, and the tail gas is made
For the circulating air of the Fischer-Tropsch synthesis.
Stoving process is by moisture removal most in low-order coal, low-order coal and exhaust gas after being dried, after drying
Low-order coal enters gasification reducing process and reacts to obtain the gas mixture of high temperature and the upgraded coal with certain temperature；Gasification
The source of oxygen is mainly in the following several ways in the anaerobic or micro- oxygen environment that reducing process uses: (1), inside raw material low-order coal
Gap, between material and material gap entrainment air；(2) from leakages such as feed inlet, the discharge ports of gasification reducing process
Mixed a small amount of air；(3), Coal Quality percentage is accounted for hereinafter, can slightly be passed through in gasification reducing process in explosion limit value
O than 5%2Or (air), further preferably it is passed through the O for accounting for Coal Quality percentage 3%2Or (air), be conducive to improve
Temperature, the slagging prevention etc. for the reduction reaction that gasifies, and ensure that the security and stability of entire gasification reducing process reaction simultaneously；
It is preferred that the low-order coal after drying carries out gasification reduction reaction in oxygen-free environment, the low-order coal after avoiding drying is entering gasification also
Combustion reaction occurs for low-order coal and oxygen after drying in original process reaction process, generates a large amount of aphlogistic CO2, to protect
Demonstrate,prove CO in the gas mixture of obtained high temperature2Volume basis it is smaller, be conducive to the subsequent synthesis gas for preparing high-energy density,
Processing step is few, simple to operation, so that reaction can carry out safely；Contain CO, H in the gas mixture of high temperature2、CO2、
Hydro carbons, dust, coal tar and sulfur-containing compound etc., by purification process except impurity such as dust, coal tar and sulfur-containing compounds
Gas, thus the mixed gas after being purified；Mixed gas mainly includes CO, H2And hydro carbons, it is well known that CO and H2It can be straight
Connect the level-one raw material as chemical industry synthesis, hydro carbons then needs reforming to generate CO and H2, therefore utilize reforming work
Part hydrocarbon reformation in mixed gas is converted to obtain comprising CO and H by skill2Reforming gas, CO and H in reforming gas2One
It is derived partly from mixed gas original CO and H2, another part obtains comprising CO and H from some hydrocarbon is reforming2,
Substantially increase CO and H in reforming gas2Total percent by volume.CO in reforming gas2Fischer Tropsch waxes are belonged to
Invalid gas, therefore the CO in reforming gas is reduced using decarbonization process as far as possible2Percent by volume, to obtain volume
Percentage bigger CO and H2, so that obtaining includes mainly CO and H2Synthesis gas.Because Fischer-Tropsch reaction synthetic wax requires synthesis
Hydrogen-carbon ratio in unstripped gas is between 1.5-2.2, it is therefore desirable to adjust the hydrogen-carbon ratio of reforming gas to obtain meeting Fischer-Tropsch
The synthesis gas of synthetic raw gas condition, the present invention in using supplement CO or H2Hydrogen-carbon ratio circle of reforming gas that makes of method
Between 1.5-2.2, as gained gas is the synthesis gas that hydrogen-carbon ratio is 1.5-2.2.Synthesis gas is made in fischer-tropsch synthetic catalyst
Fischer-Tropsch synthesis is carried out under, the gas after reaction obtains thick mink cell focus, thick light oil, heavy wax and tail by Oil-gas Separation
Gas, tail gas enter F- T synthesis as circulating air, and thick mink cell focus, thick light oil and heavy wax are produced through distillate stripping process
Product qualification wax, while the mink cell focus and naphtha of high added value can also be obtained.
Preferably, the purification process includes dust collecting process, detar technique and sulfur removal technology.The gas mixture of high temperature
In contain dust, coal tar, vapor, CO2、H2S and COS etc.；First with dust collecting process dedusting, prevent in dust removal process by
It is reduced in the temperature of gas mixture, leads to coal tar and vapor etc. to be condensed into liquid and adhere to a large amount of dusts to cause subsequent work
Skill line clogging, causes dust removing effects to decline.It recycles detar technique to remove a large amount of tar and vapor, has prevented water cooling
But it is attached in process pipe and blocks pipeline, the problems such as carbon distribution.It is further preferred that oil water mixture after cooling passes through oil again
Byproduct coal tar can be obtained in water separation.The remaining gas after detar process is finally entered sulfur removal technology again to take off
Except H2S and COS etc. avoids the catalyst poisoning in subsequent technique.
Preferably, the Fischer-Tropsch synthesis is deposited in the pressure of 1.0-4.5Mpa, 180-250 DEG C of temperature and catalyst
It carries out under the conditions.Fischer-tropsch synthesis process mainly includes high temperature fischer-tropsch synthesis and Low Temperature Fischer Tropsch synthesis at present.High temperature fischer-tropsch
Synthesis technology generally uses fluidized-bed reactor, mostly uses Fe base catalyst, and between 300-350 DEG C, pressure is about temperature
2.5MPa mainly obtains the compound of C1-C15, produces gasoline and linear low molecular weight alkene, and the selectivity of unsaturated hydrocarbons is high
Up to 67%.Low Temperature Fischer Tropsch synthesis technology generally uses fixed bed or paste state bed reactor, uses Fe base or Co base catalyst, temperature
Between 180-250 DEG C, pressure 1.0-4.5MPa, energy consumption of reaction is low, main to produce high amylose paraffin hydrocarbon, therefore
Preferred Low Temperature Fischer Tropsch synthesizes target product wax in the present invention.
Preferably, the reaction temperature of the gasification reducing process is 350-800 DEG C.At this temperature, the low order after drying
Volatile matter in coal is escaped from low-order coal, so that the gas mixture of high temperature is obtained, remaining solid after the reduction reaction that gasifies
Residue is the upgraded coal with temperature, and the volatile matter content in upgraded coal is 8-15wt%.Wherein, gasification reducing process can be one
Grade, or multistage.When using level-one gasification reducing process, primarily to obtaining the air-fuel mixture of most of high temperature
Object, the height of temperature directly affect the temperature of subsequent gas production, the yield of upgraded coal and level-one upgraded coal；When using multistage gasification
When reducing process, multistage gasification reducing process main function is the solids that can not gasify in upper level gasification reducing process
Matter (including the fine coal after gasification, solid impurity etc.), a certain amount of, can not gasifying within certain residence time, similar pitch
Equal higher boilings grease continues gasification and the residence time is short, have little time to be precipitated or phenolic compound, aromatic hydrocarbon is not achieved in temperature
The polycondensation reaction condition of compound etc., gasification that the reaction was continued are conducive to the quality for improving gas yield and upgraded coal.
Preferably, the gasification reducing process includes level-one gasification reducing process and second level gasification reducing process, will be described
Low-order coal after drying passes sequentially through level-one gasification reducing process and second level gasification reducing process handle to obtain gas mixture and
Upgraded coal.
Preferably, the mixed gas through the reforming technique of some hydrocarbon be by each component gas in mixed gas not
Being separated directly reforming by some hydrocarbon is CO and H2Hydrocarbon reformation conversion process.Because reforming purpose is only
It is in order to which the hydrocarbon conversion is generated CO and H2, reforming gas is obtained, and itself contained some CO and H in mixed gas2,
There is no need to separate hydro carbons from mixed gas to carry out the reforming of hydro carbons again, work is saved using such operation
Skill step, high financial profit.
Reforming technique includes Partial Oxidation, vapor catalyzed reforming and on-catalytic reforming converts.It urges part
Change oxidation, it is vapor catalyzed it is reforming be required to catalyst, the catalyst of reforming technique is mostly loaded catalyst, activity
Component is mainly that Ni, Co, Fe, Cu etc. be nonmetallic and the noble metals such as Rh, Ru, Pt.It is reforming to generally require heat supply, it can use
The mode of direct heating or indirect heating.CO and H in reforming gas2Source be two parts, a part be gaseous mixture
The CO and H that some hydrocarbon is obtained by catalyzed conversion in body2, another part is original H in mixed gas2And CO.
Partial Oxidation under the effect of the catalyst, is mixed using oxygen and a part of hydrocarbon fuel direct heating
It closes some hydrocarbon in gas and reacts generation CO and H with vapor2；Using extraneous heat supply when vapor catalyzed reforming, urging
It reacts some hydrocarbon and vapor in gaseous mixture and generates CO and H2；The key reaction machine of two methods
Reason are as follows:
(1)CmHn+mH2O=mCO+1/2 (n+2m) H2Main reaction, the endothermic reaction
(2)CO+H2O=CO2+H2Side reaction, the endothermic reaction
On-catalytic reforming conversion, which is reformed, does not need catalyst, key reaction mechanism are as follows: CH4+1/2O2→CO+2H2, remove methane
Other outer hydro carbons and methane and O2Reaction mechanism it is similar.
It is therefore preferred that the reforming technique is Partial Oxidation, the Partial Oxidation be by pure oxygen and
Vapor is passed through in mixed gas, part under the conditions of existing for 850-1300 DEG C of the temperature and catalyst, in mixed gas
Hydro carbons is reacted with vapor, obtains CO and H2。
Preferably, the reforming technique is vapor catalyzed reforming, described vapor catalyzed reforming for by water
Steam is passed through in mixed gas, under the conditions of indirect heating reaches temperature existing for 850-1200 DEG C and catalyst, gaseous mixture
Some hydrocarbon reacts to obtain CO and H with vapor in body2。
Preferably, the reforming technique is on-catalytic reforming conversion, and the on-catalytic reforming, which is converted into, leads to pure oxygen
Enter in mixed gas, some hydrocarbon in mixed gas reacts to obtain CO and H with pure oxygen2。
Preferably, the medium of the distillate stripping process is superheated steam, and the pressure of the superheated steam is 2.0-
2.5MPa, the temperature of the superheated steam are 350 DEG C -380 DEG C.
Based on above technical scheme, the present invention has the advantages that compared with the existing technology
1, the low order coal gasification reduction after drying is prepared into mixed gas under anaerobic or micro-oxygen conditions by the present invention, is reduced
N in mixed gas2And CO2Etc. the amount of invalid gas, CO, CH of mixed gas are improved4And H2Energy density, mixed gas
Volatile matter in low-order coal is used to produce the liquid such as light oil, mink cell focus and wax and produced by the volatile matter in low-order coal
Product, added value of product is high, is conducive to transport, to improve the utilization rate of resource.
2, low energy consumption for Low Temperature Fischer Tropsch synthesis technology, and equipment requirement is low, is conducive to save production cost.
3, the saturation degree of Fischer Tropsch waxes is high in the present invention, hardly sulfur-bearing, nitrogen, aromatic hydrocarbons, is to prepare top-grade lubricating oil base
The rare quality raw materials of plinth oil, have considerable commercial interest.
Detailed description of the invention
It, below will be in embodiment in order to illustrate more clearly of embodiment in the present invention or technical solution in the prior art
Required attached drawing is briefly described, it should be apparent that, the accompanying drawings in the following description is only one recorded in the present invention
A little embodiments are also possible to obtain other drawings based on these drawings for those of ordinary skill in the art.
Fig. 1 is a kind of flow diagram using the method for volatile matter Fischer Tropsch waxes in low-order coal.
Specific embodiment
Next combined with specific embodiments below invention is further explained, but does not limit the invention to these tools
Body embodiment.One skilled in the art would recognize that present invention encompasses may include in Claims scope
All alternatives, improvement project and equivalent scheme.
In the present invention, if not refering in particular to, used raw material and equipment etc. are commercially available or commonly used in the art.
Method in following embodiments is unless otherwise instructed the conventional method of this field.
As shown in Figure 1, the invention discloses a kind of method using volatile matter Fischer Tropsch waxes in low-order coal, low-order coal according to
Secondary to handle to obtain gas mixture by stoving process and gasification reducing process, the gasification reducing process is in anaerobic or micro- oxygen
Under the conditions of chemical reaction process that the low-order coal after drying is heated；
The purified technique of gas mixture is obtained comprising CO, H2With the mixed gas of hydro carbons；
The mixed gas is obtained through the reforming process of some hydrocarbon comprising CO and H2Reforming gas, it is described
Reforming gas handles to obtain synthesis gas by decarbonization process, by supplementing CO or H2The hydrogen-carbon ratio of the synthesis gas is adjusted to
1.5-2.2；
The synthesis gas carries out Fischer-Tropsch synthesis under fischer-tropsch synthetic catalyst effect and obtains through Oil-gas Separation technique
Thick mink cell focus, thick light oil, heavy wax and tail gas, the thick mink cell focus, thick light oil and heavy wax are through distillate stripping process
Mink cell focus, naphtha and lightweight wax are obtained, the lightweight wax handles to obtain product qualification wax through wax filtering technique, and the tail gas is made
For the circulating air of the Fischer-Tropsch synthesis.
Raw material low-order coal of the invention can be fine coal and be also possible to lump coal, when low-order coal uses lump coal, to bulk excessively
Coal can be by broken, screening process to obtain the lesser fine coal of granularity.It is preferred that using fine coal as raw material, be on the one hand because of
Fine coal is no longer needed to through broken, screening process, saves processing step, and heating surface area is big when drying, and drying efficiency is high, is on the other hand
Fine coal is cheap with respect to lump coal.It is preferred that being less than the fine coal of 20mm using granularity, still further preferably using granularity less than 6mm's
Fine coal.
Low-order coal mainly includes lignite and bituminous coal, and volatile matter content is generally 20%-55%, the content of tar in low-order coal
For 3%-15% or so, the content of fixed carbon is 30%-60%, the content of water is 10%-40%, remaining as dust etc. other
Impurity.The degree of coalification of low-order coal is low, but contains petroleum resources abundant, and the volatile matter being rich in low-order coal is to extraction synthesis gas
It is highly beneficial, therefore preferably low-order coal of the volatile matter between 30%-55%.
Drying can only generally remove most Free water in low-order coal, and cannot remove the combination water in low-order coal, because
This, low-order coal by stoving process handle after dry after low-order coal and exhaust gas, gained dry after low-order coal still contain
There is a certain amount of moisture, the moisture of this some residual can gasify in subsequent gasification reducing process becomes vapor.If low order
Contain a large amount of moisture in coal, heat consumption is big during will lead to gasification reduction reaction, and therefore, technical solution of the present invention is preferred
The portion of water first removed in low-order coal is handled by stoving process to low-order coal.The drying medium of stoving process can be
Flue gas or vapor, drying can be divided into directly drying and indirect drying.When using flue gas as medium is dried, although flue gas
The efficiency of the drying directly contacted with low-order coal is highest, but while being dried using flue gas wants strict control stoving process
For the percent by volume of oxygen in explosion limit hereinafter, to prevent detonation, the efficiency of flue gas indirect drying is also unsatisfactory in environment,
Therefore for production safety and drying efficiency, preferably vapor is dried.Vapor directly dries and is easy to be likely to result in vapor
It is mixed into and is provided with the consumption in low-order coal, not only causing reaction coal resource, reduce drying efficiency, therefore using between vapor
The drying mode of drying low-order coal is connect, to prevent the moisture in water steam from entering in low-order coal.In addition, if water in drying course
Steam pressure is excessive, and vapor bring temperature is excessively high to be easy to cause during the drying process, and part volatile matter can be escaped in low-order coal
Evolution comes, and the evolution of one side volatile matter can bring security risk, on the other hand will affect the production gas of subsequent gasification reducing process
Amount, therefore dry steam pressure in drying course and be not easy excessive, to guarantee not only to can guarantee drying effect, but also it can guarantee low-order coal
In volatile matter do not gasified.It is preferred, therefore, that stoving process uses water vapour indirect drying, the pressure of water vapour is 0.3-
1.5Mpa, the temperature of water vapour are 105-250 DEG C, can maximumlly be reduced under this process condition aqueous in low-order coal
Rate, it might even be possible to so that being reduced to 7wt% from the water content in the low-order coal that the discharge port of stoving process is discharged hereinafter, big at this time
Partial moisture is escaped from low-order coal along with fugitive dusts such as coal dusts, and is generated as water vapor into after drying useless
In gas, the outlet mass temperatures of stoving process are 50-150 DEG C；Still further preferably, when the pressure of vapor is 0.6-
1.2Mpa, when the temperature of vapor is 120-200 DEG C, the moisture content of low-order coal will decrease to 6wt% hereinafter, drying work after drying
The outlet mass temperatures of skill are 80 DEG C -130 DEG C.
Stoving process of the invention can be level-one, or it is multistage, because if low-order coal after level-one stoving process
Moisture content still reach to the requirement less than technique, can be continued using multistage dry such as second level drying, three-level stoving process into one
Drying is walked, until the moisture content of low-order coal meets process conditions after drying.In addition, multistage stoving process can be arranged in series
It can also be arranged in parallel, drying effect can be reinforced when connecting using multistage stoving process, stoving process can be increased when in parallel
Treating capacity therefore according to the demand of actual production technique be series connection to multistage stoving process or in parallel in parallel or in series
Design simultaneously, can be adjusted according to the actual situation, as long as identical technical effect can be reached, specifically, for example,
When the inlet amount of stoving process is in terms of the low-order coal of 20-30t/h, level-one steam drying technique can be used；When stoving process into
Second steam stoving process can be used in terms of the low order of 50-70t/h in doses, more economical reasonable in this way.
Preferably, the low-order coal after being dried by stoving process enters to gasification reducing process and is reacted, after the drying
Low-order coal enter gasification reducing process before can also add gasification feeding process, so as to by drying after low-order coal rapidly enter
Gasify reducing process, increases the surface area of material, is conducive to accelerate gasification reduction reaction.
Wherein, gasification reducing process is that the chemistry that is heated under anaerobic or micro-oxygen conditions to the low-order coal after drying is anti-
Answer technique.Low-order coal after drying enters gasification reducing process, under the heating of the heat mediums such as flue gas, is not necessarily in reaction process
Other substances such as additive are added, temperature is generally 350 DEG C -800 DEG C, the mistake of complex chemical reaction occurs under pressure≤30Kpa
Journey obtains the gas mixture of solid carbon and high temperature, wherein solid carbon is upgraded coal, the volatile matter 8- in upgraded coal
15wt%.The gas mixture of high temperature is to include CO, H2、CO2, hydro carbons, coal tar, the plurality of impurities gas such as dust and organic sulfur.
Wherein, the source of gasification reducing process uses anaerobic or micro- oxygen environment oxygen is mainly in the following several ways: (1),
Gap inside raw material low-order coal, the air of the gap entrainment between material and material, the O in the air of this part2Gasifying
It is reacted immediately with coal in the environment of reducing process high temperature and generates CO2Or CO；(2) from the feed inlet of gasification reducing process, discharging
The mixed a small amount of air of the leakage such as mouth, the oxygen of this partial air, the micro O in this part2In gasification reducing process high temperature
It is reacted immediately with coal under environment and generates CO2Or CO；(3), in explosion limit value hereinafter, can be slightly passed through in gasification reducing process
Account for the O of Coal Quality percentage 5%2Or (air), 1. this operation, which has the advantage that, can be improved in gasification reducing process
Temperature and capacity usage ratio；2. improving the conversion ratio of charcoal；3. preventing coal coking；4. a small amount of O2With low-order coal imperfect combustion
More CO are produced, bring more synthesis gas to be subsequent.Since gasification reducing process internal temperature is higher, what is be passed through lacks
Measure O2Moment can occur oxidation reaction (including combustion reaction), and the burning point of many combustibles is all in the reaction temperature of gasification reduction reaction
Below degree.Because CO mixes with air explosion limit 12%-74.2%；H2Explosion value is 4%-75%.O2Accounting for AIR Proportional is 21%.
The explosion limit upper value of pure oxygen is 6% or so after conversion.By theoretical calculation, the coal of 100kg can generate about 80Nm3CO and H2。
So being passed through the O for accounting for Coal Quality percentage 5%2It is safe；Still further preferably, it is passed through and accounts for Coal Quality percentage 3%
O2, with the security and stability for the reducing process reaction that ensures entirely to gasify.But when the temperature of gasification reduction reaction meets technique
It is required that when, it can not also be passed through oxygen, the low-order coal after preferably drying carries out gasification reduction reaction in oxygen-free environment, so that instead
It should be able to carry out safely.
Wherein, gasification reducing process can be level-one, or multistage.It is main when using level-one gasification reducing process
If the gas mixture of most of high temperature, the height of temperature directly affect subsequent gas production, the yield of upgraded coal in order to obtain
With the temperature of level-one upgraded coal, the reaction temperature for the reducing process that gasifies is 350 DEG C -800 DEG C, and the volatile matter content in upgraded coal is
8-15wt%, further preferably, the reaction temperature for the reducing process that gasifies are 400-750 DEG C；Still further preferably 450-700 DEG C.
When using multistage gasification reducing process, multistage gasification reducing process main function is the nothing in upper level gasification reducing process
Method gasification solid matter (including gasification after fine coal, solid impurity etc.), it is a certain amount of, can not within certain residence time gas
The higher boilings grease such as pitch change, similar continue that gasification and residence time are short, have little time to be precipitated or phenols is not achieved in temperature
The polycondensation reaction condition of compound, arene compound etc., gasification that the reaction was continued are conducive to improve gas yield and upgraded coal
Quality.
Other than the temperature of guarantee gasification reducing process is reasonable, while it must also guarantee certain in gasification reducing process stop
The time is stayed, the residence time is too short, and volatile matter also not evolution gasification completely while influencing gas yield, more influences upgrading
The quality of coal；Residence time is too long, although product is guaranteed, yield is not caught up with, so keeping a reasonable gasification
The reduction reaction residence time is most important to product yield and quality.It is general to gasify since the kind of raw material low-order coal is different
The residence time of material is 30min-4h in reducing process.
Preferably using two-stage gasification reducing process in the present invention, the material after stoving process drying is introduced into level-one gasification also
Original process enter back into second level gasification reducing process, and the low-order coal after drying is introduced into level-one gasification reducing process and obtains level-one gas
With level-one solid, level-one solid enter back into second level gasification reducing process continue gasification obtain secondary gas and second level solid, second level
Solid is upgraded coal；The feeding temperature of level-one gasification reducing process is 80 DEG C -120 DEG C, and air outlet temperature is 180 DEG C -550 DEG C,
Reaction temperature is 450 DEG C -650 DEG C, and drop temperature is 350 DEG C -600 DEG C；The feeding temperature of second level gasification reducing process is
350 DEG C -600 DEG C, drop temperature is 450 DEG C -750 DEG C, and reaction temperature is 550 DEG C -800 DEG C, and air outlet temperature is 450 DEG C -700
℃.When using two-stage gasification reducing process, primarily to most of volatile is made to be gasified totally, it can obtain a large amount of
Gas can obtain the lower upgraded coal of volatile matter again, and wherein the volatile matter content in upgraded coal is 3-8wt%.The unit of upgraded coal
Price is generally 500-600 member/T, and the upgraded coal after gasification reduction can be used for selling.Upgraded coal volatilization after second level gasification
Point lower, basic burning is smokeless, also known as anthracite, can do steel mill's sintering coal, and anthracitic commercially available price about 800-1400 member/
Ton.
The gas mixture of high temperature obtained from gasification reducing process enter purification process with remove solid dirt, tar and
Sulfur-containing compound etc. is can be obtained mixed gas.
Purification process includes dust collecting process, detar technique and sulfur removal technology, and gas mixture is successively through dust collecting process, de-
Tar technique and sulfur removal technology handle to obtain comprising CO, H2With the mixed gas of hydro carbons.Contain ash in the gas mixture of high temperature
Dirt, coal tar, vapor, CO2、H2S and COS etc.；First with dust collecting process dedusting, for example, by using cyclone dust collectors, prevent from removing
Since the temperature of gas mixture reduces during dirt, causes coal tar and vapor etc. to be condensed into liquid and adhere to a large amount of dusts
Subsequent technique line clogging is caused, dust removing effects is caused to decline.Detar technique is recycled to remove a large amount of tar and vapor,
Whose cooling has been prevented to be attached in process pipe and block pipeline, the problems such as carbon distribution.For example, detar technique uses spray column, it is cold
But oil gas.It is further preferred that oil water mixture after cooling passes through water-oil separating again can be obtained byproduct coal tar, coal tar
The unit price of oil is 2000-2500 member/T, and the value for the coal tar that richness produces is higher.It finally again will be after detar process
Remaining gas enters sulfur removal technology.Finally oil gas cooling technique treated remaining gas is made by sulfur removal technology again
The content of sulfide is reduced to 10ppm hereinafter, preventing sulfur-containing compound from causing the catalyst poisoning in subsequent reformation conversion process,
Such as dry desulfurization etc., as long as can achieve the effect that desulfurization.Foreign gas and solid can be removed using process above, so as to
Mixed gas after being purified, mixed gas impurity is few, handles convenient for subsequent technique, ensure that the stability of follow-up equipment.
In order to advanced optimize technique, if the volume fraction in gas mixture containing unsaturated hydrocarbons is excessively high, can also increase
If hydrogenation technique is translated into saturated hydrocarbons, the problems such as preventing unsaturated hydrocarbons decarburization and cause carbon distribution；Further, can also increase
If denitrating technique or dechlorination process are to realize further purification gas mixture.
Preferably gasified reducing process using two-stage in the present invention, every grade of gasification reducing process distinguish successively with respective dedusting
The connection such as technique, detar technique and sulfur removal technology；The amount of dust in high-temperature oil gas generated after every grade of gasification reduction is larger, because
This, in order to advanced optimize technique, every grade of gasification reducing process is first connect with respective dust collecting process, and every grade of dust collecting process is again
It washes technique with same set of detar technique and desulfurization to be sequentially connected, to save process procedure.
It obtains mixed gas from purification process and is handled into reforming technique to obtain comprising CO and H2Reformation
Convert gas.It wherein, include CO, H in mixed gas2、CO2With include CH4Hydro carbons etc..
In order to advanced optimize technique, mixed gas enters back into before reforming process and can first carry out compression processing and mention
The pressure of high mixed gas, convenient for the generation of reforming reaction.
Mixed gas is that each component gas in mixed gas is direct without isolation through the reforming technique of some hydrocarbon
Reforming by some hydrocarbon is CO and H2Hydrocarbon reformation conversion process.Because reforming purpose is intended merely to hydrocarbon
Class is converted into CO and H2, and itself contained some CO and H in mixed gas2, there is no need to by hydro carbons from mixed gas
It separates and carries out the reforming of hydro carbons again, processing step, high financial profit are saved using such operation.
Reforming mainly includes Partial Oxidation, the conversion of vapor catalyzed reforming and on-catalytic reforming.It urges part
Change oxidation, it is vapor catalyzed it is reforming be required to catalyst, the catalyst of reforming technique is mostly loaded catalyst, activity
Component is mainly that Ni, Co, Fe, Cu etc. be nonmetallic and the noble metals such as Rh, Ru, Pt.It is reforming to generally require heat supply, it can use
The mode of direct heating or indirect heating.CO and H in reforming gas2Source be two parts, a part be gaseous mixture
The CO and H that some hydrocarbon is obtained by catalyzed conversion in body2, another part is original H in mixed gas2And CO.
Partial Oxidation is to reach reaction temperature using oxygen (pure oxygen) and a part of hydrocarbon fuel direct heating
850-1300 DEG C, under the effect of the catalyst, some hydrocarbon in gaseous mixture is reacted with vapor generates CO and H2；Steam is urged
Using extraneous heat supply when changing reforming, so that temperature is reached 850-1200 DEG C, make in mixed gas under the effect of the catalyst
Some hydrocarbon reacted with vapor generate CO and H2；The key reaction mechanism of two methods are as follows:
(1)CmHn+mH2O=mCO+1/2 (n+2m) H2Main reaction, the endothermic reaction
(2)CO+H2O=CO2+H2Side reaction, the endothermic reaction
With CH4For, key reaction equation CH4+H2O→CO+3H2, the H of generation2Molar ratio with CO is 3:1, than
Example is larger, highly beneficial to synthesis gas is prepared.
On-catalytic reforming conversion, which is reformed, does not need catalyst, key reaction mechanism are as follows: CH4+1/2O2→CO+2H2, generation
H2Molar ratio with CO is 2:1, is conducive to prepare reforming gas.Other hydro carbons and methane and O in addition to methane2Reaction mechanism
It is similar.
Table 1: the value range of each volume components percentage in reforming preceding mixed gas:
| Component | H2 | Include CH4Hydro carbons | CO | CO2 | Other |
| Content | 15-45% | 10-52% | 5-25% | 5-25% | 0.1-10% |
Other components are N2, vapor etc., the summation of the percent by volume of each component is in reforming preceding mixed gas
100%.
Table 2: the value range of each volume components percentage in reforming rear mixed gas:
| Component | H2 | Include CH4Hydro carbons | CO | CO2 | Other |
| Content | 30-70% | 1-5% | 10-30% | 3-35% | 0.1-10% |
Other components are N2With vapor etc., it is reforming after in mixed gas the summation of the percent by volume of each component be
100%.
By Tables 1 and 2 it is found that mixed gas is after reforming process, the volume ratio of the hydro carbons in mixed gas
Percentage is reduced to 1-5% by original 10-52%, it is reforming after mixed gas in be reforming gas, reform and turn
Change the H in gas2It is greatly improved with the volume ratio percentage of CO.
Reforming gas enters decarbonization process removing CO2, CO in reforming gas2Fischer Tropsch waxes are belonged in vain
Gas, therefore the CO in reforming gas is reduced using decarbonization process as far as possible2Percent by volume, to obtain volume basis
Than bigger CO and H2, so that obtaining includes mainly CO and H2Synthesis gas.Industrial removing CO2Method it is very much, generally speaking
Two major classes can be divided into: one kind is solvent absorption, and another kind of is pressure swing adsorption method (PSA).Solvent absorption includes that physics is inhaled
Receipts method, chemical absorption method and physicochemical adsorption method, Physical Absorption method, as low-temp methanol washes method, polyethylene glycol dimethyl ether
Method, propylene carbonate ester process；Chemical absorption method, generally as NaOH, KOH, Ba (OH)2It can be very effectively Deng the stronger lye of alkalinity
Absorb CO2Gas, principle are because of CO2Gas is dissolved in water and generates carbonic acid, the hydrogen ion and lye that the ionization of carbonic acid fraction generates
In hydroxide ion reaction generate water, therefore CO can be removed2.PSA method is to utilize adsorbent to adsorbate under different partial pressures
With different adsorption capacities, adsorption rate and adsorption capacity, and under a certain pressure to by each of isolated admixture of gas
Component have selection adsorb characteristic, pressurized adsorbent remove impurities in feed gas component, these impurity of removed under reduced pressure and make adsorbent
Regenerated, the method has many advantages, such as simple process, stable operation, low energy consumption, without " three wastes " emission problem, be that a kind of energy conservation is de-
CO2New technology, have a extensive future.In addition the CO of the removing of this technique work2Also it can be recycled recycling.It is further preferred that
To synthesis gas carry out fine de-sulfur processing so that the content of the sulfide of synthesis gas be reduced to 5ppm hereinafter, fine de-sulfur for example, by using
Desulfuration adsorbent etc..Still further preferably, dewatering process, the vapor in a further removing synthesis gas are added.
Active principle in unstripped gas needed for Fischer Tropsch waxes is H2And CO, the requirement to hydrogen-carbon ratio in synthesis gas have with
Lower expression formula: R=(H2-CO2)/(CO+CO2), wherein the hydrogen-carbon ratio R=(H of unstripped gas2-CO2)/(CO+CO2) theoretical value is
2.0, optimum value 1.5-2.2.When R value is greater than 2.2, represent that the more carbon of hydrogen are few, at this time the tail gas tolerance after Fischer-Tropsch synthesis
Greatly, recycle gas compressor power consumption is big, and many unstrpped gases pass through the useful H of multiple process preparation2, CO etc. is sent into tail gas
Fuel system burn-up, causes the serious wasting of resources, and consumption of raw materials amount increases.When the R value of unstripped gas is less than 1.5, it is not able to satisfy
The requirement of Fischer Tropsch waxes.And the R value of decarbonization process treated gas cannot generally be just met for hydrogen-carbon ratio circle in 1.5-
Between 2.2, it is therefore desirable to be adjusted to its R value.Gas after decarburization generally passes through the CO or H of supplement high-purity2Do
Method is come so that hydrogen-carbon ratio circle of synthesis gas is between 1.5-2.2.
The key reaction of F- T synthesis are as follows:
Generate alkene: nCO+2nH2=CnH2n+nH2O
2nCO+nH2=CnH2n+nCO2
Generate alkane: nCO+ (2n+1) H2=CnH2n+2+nH2O
2nCO+(n+1)H2=CnH2n+2+nCO2
The reaction of side reaction is as follows:
Generate alcohols: nCO+2nH2=CnH2n+1OH+(n-1)H2O
Generate methane: CO+3H2=CH4+H2O
Generate aldehydes: (n+1) CO+ (2n+1) H2=CH2n+1+nH2O
Water gas reaction: CO+H2O=H2+CO2
Coking reaction: 2CO=C+CO2
Fischer-tropsch synthesis process is divided to two classes: high temperature fischer-tropsch synthesis and Low Temperature Fischer Tropsch synthesis at present.High temperature fischer-tropsch synthesis technology one
As use fluidized-bed reactor, mostly use Fe base catalyst, for temperature between 300-350 DEG C, pressure is about 2.5MPa, main
To the compound of C1-C15, produces gasoline and linear low molecular weight alkene, the selectivity of unsaturated hydrocarbons are up to 67%.Low temperature
Fischer-tropsch synthesis process generally uses fixed bed or paste state bed reactor, and using Fe base or Co base catalyst, temperature is at 180-250 DEG C
Between, pressure 1.0-4.5MPa, energy consumption of reaction is low, and it is main to produce high amylose paraffin hydrocarbon, therefore in the present invention preferably
Low Temperature Fischer Tropsch synthesizes target product wax.Compared with Fe base catalyst, Co base catalyst active and chain growth ability with higher,
Lower water gas shift reation, oxygenatedchemicals is few, carbon dioxide is low in product, carbon distribution is not easy in reaction process, stability is high,
The advantages such as deactivation rate is low, therefore, Co base catalyst is considered as the optimal selection of Low Temperature Fischer Tropsch synthetic reaction.
Oil-gas Separation: gas of the Low Temperature Fischer Tropsch after generating reaction is mainly hydrocarbons, solid-state or liquid scoriform object
Matter is mainly heavy wax, and hydrocarbons respectively obtain thick mink cell focus, thick light oil and tail gas after entering Oil-gas Separation process,
Tail gas can be used as circulating air and enter fischer-tropsch synthesis process, to save gas raw material, improve the utilization rate of synthesis gas.
Distillate stripping: distillate stripping mainly includes stripper and release air compressor.From Oil-gas Separation technique
Thick light oil is sent after heating to stripper middle and upper part.Heavy wax from fischer-tropsch reactor enters stripping from stripper bottom
Tower.Enter stripper middle and lower part after the thick mink cell focus that Oil-gas Separation technique is isolated is heated.Stripping fluid use pressure for
2.3-2.5MPa, the superheated steam that temperature is 350 DEG C -380 DEG C, are entered by stripper bottom.Each section of intermediate oil is from up to down
Stripping is inversely contacted with the oil gas of stripper bottom.In stripper after abundant mass transfer, heat transfer, stripper top divides each component
The gaseous stream separated out carries out Oil, Water, Gas three phase separation hereinafter, entering and stripping tower top liquid separation tank by cooling to 50 DEG C,
Releasing for isolating is deflated to release air compressor, and the light naphtha a part isolated is back to stripping tower top as phegma
Portion's tower tray, another part send low temperature oil wash unit；It isolates stripping lime set and is sent into water treatment plant.The stabilization extracted out in the middle part of stripper
Mink cell focus.The high-temperature stable wax that stripping tower bottom part separates out enters subsequent wax filtering technique.Gas is discharged by release air pressure contracting
Enter release air compressor after machine liquid separation tank liquid separation, release gas is merged into the partial tail gas after Fischer-Tropsch reaction after compression
Row removing CO2Processing.
Wax filtering: due to containing a small amount of oil-containing catalyst fines or particle from the lightweight wax that distillate strips
Heavy hydrocarbon, for the product quality for avoiding these impurity effect waxes, in the operation of 160-180 DEG C of temperature and 0.4-0.8MPa pressure
Under environment, the slag wax being discharged in the steam stripped stable wax of distillate and synthesis Fischer-Tropsch synthesis is filtered by filter
To qualified wax.
In conclusion the present invention has the advantages that compared with the existing technology
1, the low order coal gasification reduction after drying is prepared into mixed gas under anaerobic or micro-oxygen conditions by the present invention, is reduced
N in mixed gas2And CO2Etc. the amount of invalid gas, CO, CH of mixed gas are improved4And H2Energy density, mixed gas
Volatile matter in low-order coal is used to produce the liquid such as light oil, mink cell focus and wax and produced by the volatile matter in low-order coal
Product, added value of product is high, is conducive to transport, to improve the utilization rate of resource.
2, low energy consumption for Low Temperature Fischer Tropsch synthesis technology, and equipment requirement is low, is conducive to save production cost.
3, the saturation degree of Fischer Tropsch waxes is high in the present invention, hardly sulfur-bearing, nitrogen, aromatic hydrocarbons, is to prepare top-grade lubricating oil base
The rare quality raw materials of plinth oil, have considerable commercial interest.
The above, the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although referring to before
Stating embodiment, invention is explained in detail, those skilled in the art should understand that: it still can be to preceding
Technical solution documented by each embodiment is stated to modify or equivalent replacement of some of the technical features；And these
It modifies or replaces, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of method using volatile matter Fischer Tropsch waxes in low-order coal, it is characterised in that:
Low-order coal passes sequentially through stoving process and gasification reducing process handles to obtain gas mixture, and the gasification reducing process is
The chemical reaction process that the low-order coal after drying is heated under anaerobic or micro-oxygen conditions；
The purified technique of gas mixture is obtained comprising CO, H2With the mixed gas of hydro carbons；
The mixed gas is obtained through the reforming process of some hydrocarbon comprising CO and H2Reforming gas, the reformation
Conversion gas handles to obtain synthesis gas by decarbonization process, by supplementing CO or H2The hydrogen-carbon ratio of the synthesis gas is adjusted to 1.5-
2.2；
The synthesis gas carries out Fischer-Tropsch synthesis under fischer-tropsch synthetic catalyst effect and obtains through Oil-gas Separation technique big and heavy
Matter oil, thick light oil, heavy wax and tail gas, the thick mink cell focus, thick light oil and heavy wax are obtained through distillate stripping process
Mink cell focus, naphtha and lightweight wax, the lightweight wax handle to obtain product qualification wax through wax filtering technique, and the tail gas is as institute
State the circulating air of Fischer-Tropsch synthesis.
2. a kind of method using volatile matter Fischer Tropsch waxes in low-order coal as described in claim 1, it is characterised in that: described
Purification process includes dust collecting process, detar technique and sulfur removal technology.
3. a kind of method using volatile matter Fischer Tropsch waxes in low-order coal as described in claim 1, it is characterised in that: described
Fischer-Tropsch synthesis carries out under the conditions of being existing for the pressure of 1.0-4.5Mpa, 180-250 DEG C of temperature and the catalyst.
4. a kind of method using volatile matter Fischer Tropsch waxes in low-order coal as described in claim 1, it is characterised in that: described
Gasification reducing process includes level-one gasification reducing process and second level gasification reducing process, and the low-order coal after the drying is successively led to
It crosses level-one gasification reducing process and second level gasification reducing process handles to obtain gas mixture.
5. a kind of method using volatile matter Fischer Tropsch waxes in low-order coal as described in claim 1, it is characterised in that: described
The reaction temperature of gasification reducing process is 350-800 DEG C.
6. a kind of method using volatile matter Fischer Tropsch waxes in low-order coal as described in claim 1, it is characterised in that: described
Mixed gas is that each component gas in mixed gas is directly passed through part without isolation through the reforming technique of some hydrocarbon
Hydrocarbon reformation is converted into CO and H2Hydrocarbon reformation conversion process.
7. a kind of method using volatile matter Fischer Tropsch waxes in low-order coal as claimed in claim 6, it is characterised in that: described
Reforming technique is Partial Oxidation, and the Partial Oxidation is that pure oxygen and vapor are passed through in mixed gas,
Under the conditions of 850-1300 DEG C of temperature and catalyst is existing, some hydrocarbon in mixed gas is reacted with vapor, obtains CO
And H2。
8. a kind of method using volatile matter Fischer Tropsch waxes in low-order coal as claimed in claim 6, which is characterized in that described
Reforming technique be it is vapor catalyzed reforming, it is described vapor catalyzed reforming for vapor to be passed through in mixed gas,
Under the conditions of indirect heating reaches temperature existing for 850-1200 DEG C and catalyst, some hydrocarbon and vapor in mixed gas
Reaction obtains CO and H2。
9. a kind of method using volatile matter Fischer Tropsch waxes in low-order coal as claimed in claim 6, it is characterised in that: described
Reforming technique is on-catalytic reforming conversion, and the on-catalytic reforming, which is converted into, is passed through pure oxygen in mixed gas, gaseous mixture
Some hydrocarbon in body reacts to obtain CO and H with pure oxygen2。
10. a kind of method using volatile matter Fischer Tropsch waxes in low-order coal as described in claim 1, it is characterised in that: institute
The medium for stating distillate stripping process is superheated steam, and the pressure of the superheated steam is 2.0-2.5MPa, the superheated steam
Temperature be 350 DEG C -380 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910105628.0A CN109880654A (en) | 2019-02-01 | 2019-02-01 | A method of utilizing volatile matter Fischer Tropsch waxes in low-order coal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910105628.0A CN109880654A (en) | 2019-02-01 | 2019-02-01 | A method of utilizing volatile matter Fischer Tropsch waxes in low-order coal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109880654A true CN109880654A (en) | 2019-06-14 |
Family
ID=66927885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910105628.0A Pending CN109880654A (en) | 2019-02-01 | 2019-02-01 | A method of utilizing volatile matter Fischer Tropsch waxes in low-order coal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109880654A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110982557A (en) * | 2019-12-09 | 2020-04-10 | 河北理查德农业科技有限公司 | Method for synthesizing oil by using crop straws |
| CN111484867A (en) * | 2020-05-25 | 2020-08-04 | 中国石油大学(北京) | Skid-mounted light hydrocarbon recovery device and method |
| CN112094663A (en) * | 2020-08-03 | 2020-12-18 | 国家能源集团宁夏煤业有限责任公司 | Method and device for separating Fischer-Tropsch synthesis product |
| CN114806624A (en) * | 2021-01-27 | 2022-07-29 | 国家能源投资集团有限责任公司 | Method and system for preparing hydrocarbons from synthesis gas |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424359A (en) * | 2011-08-26 | 2012-04-25 | 北京大学深圳研究生院 | Method for preparing synthetic gas by three-phase type biomass pyrolysis-gasification-catalytic reforming |
| CN102911756A (en) * | 2012-10-26 | 2013-02-06 | 太原理工大学 | Technology for producing methane through low-rank coal |
| CN104893748A (en) * | 2015-06-16 | 2015-09-09 | 西安元创化工科技股份有限公司 | Method for producing tar and hydrocarbon fuel products from coal |
| CN105001899A (en) * | 2015-07-07 | 2015-10-28 | 新疆帕拉菲精细化工股份有限公司 | Method for preparing clean coal-based synthetic wax |
-
2019
- 2019-02-01 CN CN201910105628.0A patent/CN109880654A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424359A (en) * | 2011-08-26 | 2012-04-25 | 北京大学深圳研究生院 | Method for preparing synthetic gas by three-phase type biomass pyrolysis-gasification-catalytic reforming |
| CN102911756A (en) * | 2012-10-26 | 2013-02-06 | 太原理工大学 | Technology for producing methane through low-rank coal |
| CN104893748A (en) * | 2015-06-16 | 2015-09-09 | 西安元创化工科技股份有限公司 | Method for producing tar and hydrocarbon fuel products from coal |
| CN105001899A (en) * | 2015-07-07 | 2015-10-28 | 新疆帕拉菲精细化工股份有限公司 | Method for preparing clean coal-based synthetic wax |
Non-Patent Citations (3)
| Title |
|---|
| 内蒙古公安消防总队编著: "《煤化工事故处置实用手册》", 31 January 2018 * |
| 张德祥主编: "《煤化工工艺学》", 30 September 1999 * |
| 戴和武等主编: "《褐煤利用技术》", 28 February 1999 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110982557A (en) * | 2019-12-09 | 2020-04-10 | 河北理查德农业科技有限公司 | Method for synthesizing oil by using crop straws |
| CN111484867A (en) * | 2020-05-25 | 2020-08-04 | 中国石油大学(北京) | Skid-mounted light hydrocarbon recovery device and method |
| CN112094663A (en) * | 2020-08-03 | 2020-12-18 | 国家能源集团宁夏煤业有限责任公司 | Method and device for separating Fischer-Tropsch synthesis product |
| CN114806624A (en) * | 2021-01-27 | 2022-07-29 | 国家能源投资集团有限责任公司 | Method and system for preparing hydrocarbons from synthesis gas |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109880654A (en) | A method of utilizing volatile matter Fischer Tropsch waxes in low-order coal | |
| CN102517108A (en) | Technology for preparing liquefied natural gas and liquid ammonia by using coke oven gas | |
| CN110055104A (en) | A kind of method that the utilization of low-order coal sub-prime prepares natural gas | |
| CN104803819B (en) | A kind of method and system utilizing fine coal preparing ethylene | |
| CN101538473A (en) | Incoherence or weak caking coal deep processing method | |
| CN101979472A (en) | Method for preparing synthesis gas from carbon dioxide serving as pressurized fixed bed gasifying agent instead of water vapor | |
| CN109762603A (en) | A method of ammonia is synthesized using low-order coal multipath | |
| CN110055106B (en) | Method for preparing methanol and oil by poly-generation through low-rank coal quality-based utilization | |
| CN110862841B (en) | Method for preparing natural gas from coal water slurry | |
| CN105111107B (en) | A kind of technique of coal low-carbon alcohols and Utilization of Carbon Dioxide | |
| CN110862844A (en) | Method for preparing natural gas and co-producing hydrogen from rich gas by using low-rank coal according to quality | |
| CN110002933B (en) | Method for preparing methanol and low-carbon olefin by poly-generation through low-rank coal quality-based utilization | |
| CN110055107A (en) | A kind of method that low-order coal sub-prime utilizes technique waste water zero-emission | |
| CN105037086A (en) | Multistage utilization technology for preparing low-carbon mixed alcohol from coal through synthesis gas | |
| CN105176566B (en) | A kind of coal base artificial oil coproduction LNG method | |
| CN109762604A (en) | A method of utilizing low-order coal Fischer Tropsch waxes | |
| CN110093174A (en) | A kind of method of low-order coal hydrogen manufacturing | |
| CN105018165A (en) | Production method for natural gas | |
| CN112961711A (en) | System and method for preparing LNG (liquefied Natural gas) and coproducing methanol, liquid ammonia and hydrogen through coke oven gas purification | |
| CN109762612A (en) | A method of using waste water water-coal-slurry and passing through water-coal-slurry methanol | |
| Khadzhiev et al. | The first commercial Fischer-Tropsch processes in Germany | |
| CN110055108A (en) | A kind of method that low-order coal sub-prime is oily using preparation | |
| CN110903853B (en) | Method for preparing natural gas and co-producing hydrogen | |
| CN110669542A (en) | Method and device for preparing Fischer-Tropsch wax by using coke oven gas | |
| CN115125044B (en) | Method for preparing oil product and co-producing electricity by using low-rank coal and natural gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190614 |
|
| RJ01 | Rejection of invention patent application after publication |